Polymers from propoxylated allyl alcohol

ABSTRACT

Propoxylated allyl alcohol homopolymers and copolymers of allyl alcohol and propoxylated allyl alcohol are disclosed. The polymers are soluble in many organic solvents, making them useful in a variety of applications, including polyesters, polyurethanes, alkyds, uralkyds, polyamines, acrylates, crosslinked polymeric resins, and polymer blends.

FIELD OF THE INVENTION

The invention relates to polymers derived from propoxylated allylalcohol. In particular, the invention involves propoxylated allylalcohol homopolymers, and copolymers derived from allyl alcohol andpropoxylated allyl alcohol. The polymers and copolymers of the inventionare useful in a variety of applications, including polyesters,polyurethanes, alkyds, uralkyds, polyamines, acrylates, crosslinkedthermoset polymers, and polymer blends.

BACKGROUND OF THE INVENTION

Allyl alcohol, which is available commercially from isomerization ofpropylene oxide, is widely used to make allyl ether, ester, andcarbonate derivatives such as, for example, diallyl phthalate anddiethylene glycol bis(allyl carbonate).

Poly(allyl alcohol) is known, but it is difficult to prepare, and itsusefulness is limited by its poor solubility in most common organicsolvents. For example, poly(allyl alcohol) is soluble in alcohols, butis generally insoluble in ethers, esters, ketones, glycol ethers, andhydrocarbons. Solubility in water is also poor, except for hot water.Consequently, poly(allyl alcohol) has limited utility as a chemicalintermediate.

Copolymerization of allyl alcohol with vinyl monomers is a potential wayto make polymers having a high content of primary hydroxyl groups. Allylalcohol copolymerizes with some vinyl monomers. However, because allylalcohol is typically much less reactive than most common vinyl monomers(such as styrene), it is difficult to prepare allyl alcohol copolymersthat incorporate a useful proportion of allyl alcohol recurring units.See, for example, U.S. Pat. Nos. 2,894,938 and 2,940,946. Thus, fewallyl alcohol copolymers are widely used commercially in spite of therecognized value of polymers having a high content of primary hydroxylgroups.

Propoxylated allyl alcohol can be made by reacting allyl alcohol withpropylene oxide in the presence of a basic catalyst, as described forexample, in U.S. Pat. Nos. 3,268,561 and 4,618,703, and in J. Am. Chem.Soc. 71 (1949) 1152. Adjusting the ratio of allyl alcohol and propyleneoxide to keep the average number of oxypropylene units in thepropoxylated allyl alcohol at less than about 2 gives propoxylated allylalcohol that is readily purified by distillation. In copendingapplication Ser. No. 08/098,114, we described copolymers of thesepropoxylated allyl alcohols and vinyl aromatic monomers, and the use ofthe copolymers for polyurethanes, coatings, and unsaturated polyesters.

Still needed in the art are new hydroxyl-containing polymers. Inparticular, formulators need polymers that have a high concentration ofhydroxyl groups, yet still maintain good solubility in water and/or awide range of common organic solvents. Preferably, the polymers could beeasily prepared, and would overcome the solubility limitations ofavailable hydroxyl-containing polymers such as poly(allyl alcohol). Theability to adjust the solubility characteristics of the polymers to suita particular end use would be valuable, and would greatly expand thepotential use of these polymers in many polymer applications, such aspolyurethanes, polyesters, alkyds, uralkyds, polyamines, and acrylates.

SUMMARY OF THE INVENTION

The invention is a propoxylated allyl alcohol polymer. In one aspect,the invention is a polymer that consists essentially of recurring unitsof a propoxylated allyl alcohol. The propoxylated allyl alcohol monomerhas the formula:

    CH.sub.2 ═CH--CH.sub.2 --(A).sub.n --OH

in which A is an oxypropylene group, and n, which is the average numberof oxypropylene groups in the propoxylated allyl alcohol, has a valueless than or equal to 5. The polymer has an average hydroxylfunctionality within the range of about 2 to about 10, and a numberaverage molecular weight within the range of about 300 to about 5,000.

The invention includes copolymers which comprise recurring units ofallyl alcohol and propoxylated allyl alcohol. These copolymers also havean average hydroxyl functionality within the range of about 2 to about10, and a number average molecular weight within the range of about 300to about 5,000.

The polymers and copolymers of the invention are easier to prepare thanpoly(allyl alcohol). In addition, the compositions of the invention havefavorable solubility profiles. Because they are soluble in a relativelybroad range of common organic solvents, the polymers and copolymers ofthe invention can be formulated into a wide variety of end uses,including polyesters, polyurethanes, crosslinked thermoset polymers,alkyds, uralkyds, polyamines, and acrylates. The solubilities of thepolymers are easily adjusted by controlling the proportion ofpropoxylated allyl alcohol recurring units in the polymers.

DETAILED DESCRIPTION OF THE INVENTION

The invention relates to polymers derived from propoxylated allylalcohol. Suitable propoxylated allyl alcohols have the formula:

    CH.sub.2 ═CH--CH.sub.2 --(A).sub.n --OH

in which A is an oxypropylene group, and n, which is the average numberof oxypropylene groups in the propoxylated allyl alcohol, has a valuewithin the range of about 1 to 5. The oxypropylene groups in thepropoxylated allyl alcohols have one or both of the structures--OCH(CH₃)--CH₂ -- and --OCH₂ --CH(CH₃)--, which will depend on themethod of synthesis. Suitable propoxylated allyl alcohols can beprepared by reacting allyl alcohol with up to 5 equivalents of propyleneoxide in the presence of a basic catalyst as described, for example, inU.S. Pat. Nos. 3,268,561 and 4,618,703, the teachings of which areincorporated herein by reference herein in their entirety. As will beapparent to those skilled in the art, suitable propoxylated allylalcohols can also be made by acid catalysis, as described, for examplein J. Am. Chem. Soc. 71 (1949) 1152. Preferred propoxylated allylalcohols are those for which n has a value within the range of about 1to about 2.

The invention includes polymers that consist essentially of recurringunits of the propoxylated allyl alcohol monomers described above. Thesepropoxylated allyl alcohol polymers will have average hydroxylfunctionalities within the range of about 2 to about 10. A preferredrange is from about 3 to about 6; most preferred is the range from about4 to about 6.

The propoxylated allyl alcohol polymers of the invention will havenumber average molecular weights within the range of about 300 to about5000. A more preferred range is from about 500 to about 5000; mostpreferred is the range from about 1000 to about 5000.

We have found that propoxylated allyl alcohol polymers with the averagehydroxyl functionalities and number average molecular weights describedabove are easily manufactured, and are well-suited for use as chemicalintermediates in broad range of end uses because of their high contentof hydroxyl groups and favorable solubility profiles.

The invention also includes copolymers which comprise recurring units ofallyl alcohol and propoxylated allyl alcohol monomers. Suitablepropoxylated allyl alcohols have already been described. Any desiredgrade of allyl alcohol can be used; technical and commercially availablegrades will suffice for most purposes.

The copolymers of allyl alcohol and propoxylated allyl alcohol will haveaverage hydroxyl functionalities within the range of about 2 to about10. A preferred range is from about 3 to about 6; most preferred is therange from about 4 to about 6. The copolymers will have number averagemolecular weights within the range of about 300 to about 5000. A morepreferred range is from about 500 to about 5000; most preferred is therange from about 1000 to about 5000.

The proportions of allyl alcohol and propoxylated allyl alcoholrecurring units in the copolymers of the invention can vary broadly. Theability to make a wide spectrum of different products is a valuable toolfor controlling the solubility of the copolymers in water and variousorganic solvents. Generally, the copolymers will have from about 1 toabout 99 wt. % of allyl alcohol recurring units, and from about 99 toabout 1 wt. % of propoxylated allyl alcohol recurring units. Morepreferred copolymers will have from about 10 to about 85 wt. % of allylalcohol recurring units, and from about 90 to about 15 wt. % ofpropoxylated allyl alcohol recurring units. Most preferred copolymerswill have from about 25 to about 75 wt. % allyl alcohol recurring units,and from about 75 to about 25 wt. % of propoxylated allyl alcoholrecurring units.

The propoxylated allyl alcohol polymers and copolymers of the inventionare made by free-radical polymerization. The monomers can be simplycombined and heated in the presence of a free-radical initiator at atemperature effective to polymerize the monomers. Suitable free-radicalinitiators are the peroxide and azo-type initiators well known to thoseskilled in the art. Peroxide initiators are preferred. Examples includehydrogen peroxide, benzoyl peroxide, di-tert-butylperoxide,tert-butylhydroperoxide, tert-butylperbenzoate, azobis(isobutyronitrile)(AIBN), and the like.

Although the monomers can be simply combined and polymerized, we foundthat improved yields can be achieved if the initiator is added graduallyto the polymerization mixture during the course of the polymerization.Thus, it is preferred to introduce the initiator either continuously orintermittently to the polymerization reaction mixture.

The process can be performed at any temperature effective to initiatefree-radical polymerization. Generally, it is preferred to perform thereaction at a temperature within the range of about 90° C. to about 200°C. A more preferred range is from about 125° C. to about 180° C.; mostpreferred is the range from about 135° C. to about 165° C.

The polymerizations can be performed at any suitable pressure.Generally, it is preferred to perform the polymerization at pressuresgreater than 1 atmosphere, particularly when allyl alcohol is areactant. Particularly preferred is the pressure range from about 20 toabout 500 psi.

Optionally, a solvent is included in the polymerization. Suitablesolvents are those in which the monomers, free-radical initiator, andpolymeric reaction products are soluble. Preferred solvents for thepolymerization include alcohols, ethers, esters, glycols, glycol ethers,and glycol ether esters. Hydrocarbons are generally not suitable becausethe polymer products are usually not soluble in hydrocarbons.

Compared with poly(allyl alcohol), the propoxylated allyl alcoholpolymers and the allyl alcohol/propoxylated allyl alcohol copolymers ofthe invention are soluble in a broader range of organic solvents.Poly(allyl alcohol) is generally soluble in alcohols, but is not solublein many commonly used organic solvents such as ethers, esters, ketones,and hydrocarbons (see Table 2, Polymer B). In contrast, the polymers andcopolymers of the invention, which are derived at least partially frompropoxylated allyl alcohol, are soluble in a broad range of solvents(Table 2, Polymers C through H). Propoxylated allyl alcohol homopolymersare even soluble in esters and hydrocarbons (Table 2, Polymer A). Theimproved solubility characteristics of the polymers and copolymers ofthe invention in organic solvents give formulators of adhesives,coatings, elastomers, and sealants greater flexibility. Interestingly,some types of propoxylated allyl alcohol copolymers also appear to haveimproved water solubility (see Polymer E), which suggests their use inwater-based applications.

Propoxylated allyl alcohol polymers and copolymers are useful in avariety of applications, including, for example, polyesters,polyurethanes, alkyds, uralkyds, polyamines, acrylates, crosslinkedthermoset polymers, and polymer blends. Some of these uses are describedin detail in the description below and in the examples.

The invention includes thermoset polyester compositions prepared byreacting a propoxylated allyl alcohol polymer or copolymer with ananhydride or a di- or polycarboxylic acid. The use of such a reaction tomake a non-solvent thermoset polyester adhesive is shown in Example 9below, while Example 14 illustrates a thermosetting polyester coatingcomposition. Suitable anhydrides and carboxylic acids are those commonlyused in the polyester industry. Examples include, but are not limitedto, phthalic anhydride, phthalic acid, maleic anhydride, maleic acid,adipic acid, isophthalic acid, terephthalic acid, sebacic acid, succinicacid, trimellitic anhydride, and the like, and mixtures thereof. Othersuitable methods for making thermoset polyester compositions aredescribed in U.S. Pat. No. 3,457,324, the teachings of which areincorporated herein by reference.

A polyurethane composition is made by reacting a propoxylated allylalcohol polymer or copolymer of the invention with a di- orpolyisocyanate or an isocyanate-terminated prepolymer. Prepolymersderived from the propoxylated allyl alcohol polymers of the inventionand a di- or polyisocyanate can be used. Optionally, a low-molecularweight chain extender (diol, diamine, or the like) is included. Suitabledi- or polyisocyanates are those well known in the polyurethaneindustry, and include, for example, toluene diisocyanate, MDI, polymericMDIs, carbodiimide-modified MDIs, hydrogenated MDIs, isophoronediisocyanate, and the like. Isocyanate-terminated prepolymers are madein the usual way from a di- or polyisocyanate and a polyether polyol,polyester polyol, or the like. The polyurethane is formulated at anydesired NCO index. If desired, all of the available NCO groups arereacted with hydroxyl groups from the propoxylated allyl alcohol polymerand any chain extenders. Alternatively, an excess of NCO groups remainin the product, as in a moisture-cured polyurethane. Many types ofpolyurethanes products can be made, including, for example, adhesives,coatings, sealants, and elastomers. Example 10 illustrates a non-solventpolyurethane adhesive prepared from an isocyanate-terminated prepolymerand an allyl alcohol/propoxylated allyl alcohol copolymer. Othersuitable methods for making polyurethane compositions are described inU.S. Pat. No. 2,965,615, the teachings of which are incorporated hereinby reference.

The invention also includes alkyd compositions prepared by reacting thepropoxylated allyl alcohol polymers and copolymers of the invention withan unsaturated fatty acid. Suitable unsaturated fatty acids are thoseknown in the art as useful for alkyd resins, and include, for example,oleic acid, ricinoleic acid, linoleic acid, licanic acid, and the like,and mixtures thereof. Mixtures of unsaturated fatty acids and saturatedfatty acids such as lauric acid or palmitic acid can also be used. Thealkyd resins are particularly useful for making alkyd coatings. Forexample, a propoxylated allyl alcohol polymer, or a mixture of thepropoxylated allyl alcohol polymer and glycerin or another low molecularweight polyol, is first partially esterified with an unsaturated fattyacid to give an alkyd resin. The resin is then combined with an organicsolvent, and the resin solution is stored until needed. A drying agentsuch as lead acetate or cobalt acetate is added to the solution of alkydresin, the solution is spread onto a surface, the solvent evaporates,and the resin cures leaving an alkyd coating of the invention. Example15 below shows one way to make an alkyd coating of the invention. Othersuitable methods for making alkyd resins and coatings are described inU.S. Pat. No. 3,423,341, the teachings of which are incorporated hereinby reference.

Instead of combining the alkyd resin with an organic solvent, the resincan be dispersed in water to make a water-based alkyd coatingformulation. To improve the water dispersability of the alkyd resin, afree hydroxyl group in the alkyd resin can be converted to a salt. Forexample, the alkyd resin can be reacted with phthalic anhydride to givea resin that contains phthalic acid residues; addition of sodiumhydroxide makes the sodium phthalate salt, and provides awater-dispersable alkyd resin derived from the propoxylated allylalcohol polymer or copolymer. See, for example, U.S. Pat. No. 3,483,152.

The invention includes polyurethane-modified alkyd compositions(uralkyds) prepared from the propoxylated allyl alcohol polymers andcopolymers. These resins are especially valuable for making uralkydcoatings. The propoxylated allyl alcohol polymer or copolymer is firstpartially esterified with an unsaturated fatty acid (described above) togive an alkyd resin. The alkyd resin, which contains some free hydroxylgroups, is reacted with a di- or polyisocyanate (described above) togive a prepolymer. The prepolymer is then reacted with a chain extender,atmospheric moisture, or additional alkyd resin to give a uralkydcoating. Other suitable methods for making uralkyd resins and coatingsare described in U.S. Pat. No. 3,267,058, the teachings of which areincorporated herein by reference.

The invention includes crosslinked thermoset polymers prepared byreacting the propoxylated allyl alcohol polymers and copolymers of theinvention with a thermoplastic polymer or a crosslinking agent. Forexample, melamine-based polymers, especially coatings, can be preparedby reacting the propoxylated allyl alcohol polymers and copolymers ofthe invention with melamine resins. Suitable melamine resins includecommercial grade hexamethoxymethylmelamines, such as, for example CYMEL303 crosslinking agent, a product of American Cyanamid Company. Athermoset resin composition is obtained by reacting the propoxylatedallyl alcohol polymer with a crosslinkable thermoplastic resin. Suitablecrosslinkable thermoplastic resins are anhydride or carboxylicacid-containing polymers such as, for example, polyacrylic acid,polymethacrylic acid, isobutylenemaleic anhydride copolymers, andstyrene-maleic anhydride copolymers. Example 11 below illustrates thiskind of process.

Polyamine compositions of the invention are the reaction products of thepropoxylated allyl alcohol polymers or copolymers with ammonia or aprimary or secondary amine. Some or all of the hydroxyl groups of thepropoxylated allyl alcohol polymer are converted to primary, secondary,or tertiary amino groups by catalytic amination or any other suitabletechnique. A typical amination procedure is described in Example 12below. A suitable amination method is also described, for example, inU.S. Pat. No. 4,070,530, the teachings of which are incorporated hereinby reference.

An acrylate composition of the invention is prepared by reacting some orall of the hydroxyl groups of the propoxylated allyl alcohol polymers orcopolymers with an acrylic acid or an acrylic acid derivative. Suitableacrylic acids and derivatives include acrylic acid, methacrylic acid,acryloyl chloride, methacryloyl chloride, methyl acrylate, methylmethacrylate, and the like. Example 13 below illustrates thisapplication. Suitable methods for preparing acrylates are described, forexample, in U.S. Pat. No. 2,917,538, the teachings of which areincorporated herein by reference.

The favorable solubility characteristics of the propoxylated allylalcohol polymers and copolymers of the invention make them well-suitedfor blending with other polymers. The polymers of the invention areeasily blended with, for example, polyether polyols, phenolic resins,and epoxy resins, and the blends can be used in the applicationsdescribed earlier. The propoxylated allyl alcohol polymers andcopolymers of the invention can also be used as compatibilizers toimprove the miscibility of polymer mixtures. In contrast, poly(allylalcohol) is generally not compatible with other polymers, and cannot beblended with polymers or used as a compatibilizer for other polymers.

The following examples merely illustrate the invention. Those skilled inthe art will recognize many variations that are within the spirit of theinvention and scope of the claims.

Example 1. Preparation of Propoxylated Allyl Alcohol Homopolymer(Polymer A)

A one-liter stainless-steel reactor equipped with a mechanical stirrer,steam heating jacket, temperature controller, and inlets for nitrogenand vacuum, is charged with propoxylated allyl alcohol (average of 1.6oxypropylene units, 500 g) and di-tert-butylperoxide (15 g). The reactoris purged three times with nitrogen and sealed, and the contents areheated to 165° C. Additional di-tert-butylperoxide (40 g) iscontinuously added to the reactor over 2 h. Heating continues at 165° C.for 0.5 h after completing the peroxide addition. The mixture is vacuumstripped to remove most of the unreacted monomer, and is then strippedin the presence of water (2%) to remove traces of unreacted monomer at amaximum temperature of 185° C. The product (371 g), a homopolymer ofpropoxylated allyl alcohol, has Mn=1160, Mw=2450, and is soluble in awide range of organic solvents (see Table 2).

Comparative Example 2. Preparation of Poly(Allyl Alcohol) (Polymer B)

The procedure of Example 1 is generally followed. The reactor isinitially charged with allyl alcohol (432 g). After heating to 150° C.,di-tert-butylperoxide (61 g) is continuously added to the reactor over 4h. Heating continues at 150° C. for 0.5 h after completing the peroxideaddition. The product is stripped as described above at a maximum of160° C. to remove unreacted monomers. The product (121 g), poly(allylalcohol), has relatively limited solubility in organic solvents (seeTable 2).

Example 3: Preparation of Allyl Alcohol/Propoxylated Allyl AlcoholCopolymer: Gradual Addition of the Initiator (Polymer C)

The procedure of Example 1 is generally followed. The reactor is chargedwith propoxylated allyl alcohol (average of 1.0 oxypropylene units, 134g) and allyl alcohol (134 g). The reactor is heated to 150° C., anddi-tert-butylperoxide (55 g) is added to the reactor continuously over2.5 h. The product is stripped as described above at a maximum of 165°C. to remove unreacted monomers. A copolymer of allyl alcohol andpropoxylated allyl alcohol (149 g) is isolated and characterized (seeTables 1 and 2). The yield obtained is 56% based on the weight ofcharged monomers.

Comparative Example 4: Preparation of Allyl Alcohol/Propoxylated AllylAlcohol Copolymer: All of the Initiator Charged at the Start of thePolymerization (Polymer D)

The procedure of Example 3 is generally followed, except that all of therequired di-tert-butylperoxide is added at the start of thepolymerization. The reactor is charged with propoxylated allyl alcohol(average of 1.0 oxypropylene units, 200 g) and allyl alcohol (200 g).The reactor is heated to 155° C. for 6.5 h. The product is stripped asdescribed above at a maximum of 165° C. to remove unreacted monomers. Acopolymer of allyl alcohol and propoxylated allyl alcohol (69 g) isisolated and characterized (see Tables I and 2). The yield obtained is17% based on the weight of charged monomers.

The results of Example 3 and Comparative Example 4 demonstrate thathigher yields of copolymers result when the free-radical initiator isgradually added during the course of the polymerization.

Examples 5-8. Preparation of Allyl Alcohol/ Propoxylated Allyl AlcoholCopolymers Example 5. (Polymer E)

The procedure of Example 3 is generally followed. The reactor is chargedwith propoxylated allyl alcohol (average of 1.0 oxypropylene units, 276g) and allyl alcohol (92 g). The reactor is heated to 150° C., anddi-tert-butylperoxide (55 g) is added to the reactor continuously over 4h. The product is stripped as described above at a maximum of 165° C. toremove unreacted monomers. A copolymer of allyl alcohol and propoxylatedallyl alcohol (153 g) is isolated and characterized (see Tables 1 and2).

Example 6. (Polymer F)

The procedure of Example 3 is generally followed. The reactor is chargedwith propoxylated allyl alcohol (average of 1.0 oxypropylene units, 75g) allyl alcohol (225 g), and di-tert-butylperoxide (10 g). The reactoris heated to 150° C., and the remaining di-tert-butylperoxide (40 g) isadded to the reactor continuously over 2.5 h. The product is stripped asdescribed above at a maximum of 165° C. to remove unreacted monomers. Acopolymer of allyl alcohol and propoxylated allyl alcohol (160 g) isisolated and characterized (see Tables 1 and 2).

Example 7. (Polymer G)

The procedure of Example 3 is generally followed. The reactor is chargedwith propoxylated allyl alcohol (average of 1.6 oxypropylene units, 167g) allyl alcohol (500 g), and di-tert-butylperoxide (20 g). The reactoris heated to 165° C., and the remaining di-tert-butylperoxide (80 g) isadded to the reactor continuously over 4 h. The product is stripped asdescribed above at a maximum of 200° C. to remove unreacted monomers. Acopolymer of allyl alcohol and propoxylated allyl alcohol (173 g) isisolated and characterized (see Tables 1 and 2).

Example 8. (Polymer H)

The procedure of Example 3 is generally followed. The reactor is chargedwith propoxylated allyl alcohol (average of 1.6 oxypropylene units, 300g) allyl alcohol (300 g), and di-tert-butylperoxide (20 g). The reactoris heated to 165° C., and the remaining di-tert-butylperoxide (70 g) isadded to the reactor continuously over 3.5 h. The product is stripped asdescribed above at a maximum of 200° C. to remove unreacted monomers. Acopolymer of allyl alcohol and propoxylated allyl alcohol (319 g) isisolated and characterized (see Tables 1 and 2).

Example 9. Preparation of a Thermoset Polyester Composition

This example illustrates the preparation of a non-solvent adhesive byreacting an allyl alcohol/propoxylated allyl alcohol copolymer withphthalic anhydride. Copolymer F, prepared as in Example 6 (10 g), isheated to 80° C. to give a free-flowing liquid, and is mixed withphthalic anhydride (1.0 g). After the phthalic anhydride dissolvescompletely, the resulting adhesive mixture is used to bond two pieces ofwood, stainless steel, or glass coupons. The bonded samples are cured at180° C. for 6 h. In each case, good adhesion results.

Example 10. Preparation of a Polyurethane Composition

This example illustrates the preparation of a non-solvent polyurethaneadhesive by reacting an allyl alcohol/propoxylated allyl alcoholcopolymer with an isocyanate-terminated prepolymer.

Copolymer D, prepared as in Comparative Example 4 (10 g), is mixed wellat room temperature with 10 g of a prepolymer (5.7 wt. % free NCO)prepared from ARCOL 3020 polyether triol (2000 mol. wt., all-PO triol,product of ARCO Chemical Co.), and toluene diisocyanate. The resultingadhesive mixture is used to bond pieces of wood, stainless steel, glass,and polystyrene plastic. The bonded samples are cured at roomtemperature for 4 h. In each case, good adhesion results.

Example 11. Preparation of a Thermoset Resin Composition

In this example, an allyl alcohol/propoxylated allyl alcohol copolymeris reacted with a crosslinkable thermoplastic resin to produce athermoset resin composition.

DYLARK 378 resin (a terpolymer of styrene (67%), maleic anhydride (13%),and butadiene rubber (20%), product of ARCO Chemical Co., 10 g) andCopolymer C (2 g, prepared as in Example 3) are dissolved intetrahydrofuran (50 g). The solution is spread and dried on an aluminumpan. The resulting polymer film is cured at 200° C. for 0.5 h. The curedfilm is not soluble in tetrahydrofuran.

                                      TABLE 1                                     __________________________________________________________________________    Propoxylated Allyl Alcohol Polymers: Identification and Characterization         Polymer               Ave. # AA/AAP        % Yield                         Ex.                                                                              (see            Charged                                                                             PO     found in                                                                            Mn  Mw  of                              #  Table 1)                                                                           Type       AA/AAP                                                                              units in AAP                                                                         product.sup.1                                                                       (GPC)                                                                             (GPC)                                                                             polymer                         __________________________________________________________________________    1  A    AAP homopolymer                                                                          --    1.6    --    1160                                                                              2450                                                                              74                              C2 B    Poly(allyl alcohol)                                                                      --    --     --    *   *   28                              3  C    AA/AAP copolymers                                                                        50/50 1.0    56/44 1000                                                                              3030                                                                              56                              C4**                                                                             D               50/50 1.0    46/54 610 980 17                              5  E               25/75 1.0    51/49 720 1140                                                                              42                              6  F               75/25 1.0    89/11 580 1160                                                                              53                              G                  75/25 1.6    91/9  560 940 26                              8  H               50/50 1.6    83/17 910 2360                                                                              53                              __________________________________________________________________________     *Polymer not soluble: molecular weight not measured.                          **All of the initiator added at the start of the polymerization.              .sup.1 As measured by .sup.13 C NMR spectroscopy.                             AAP homopolymer = propoxylated allyl alcohol homopolymer;                     AA/AAP copolymer = copolymer of propoxylated allyl alcohol and allyl          alcohol.                                                                 

                                      TABLE 2                                     __________________________________________________________________________    Solubility Data for Propoxylated Allyl Alcohol Polymers                              Polymer A                                                                           Polymer B*                                                                           Polymer C                                                                           Polymer D                                                                           Polymer E                                                                           Polymer F                                                                           Polymer G                                                                           Polymer                     __________________________________________________________________________                                                      H                           MeOH,  sol   sol    sol   sol   sol   sol   sol   sol                         EtOH, IPA,                                                                    PG, EB                                                                        PTB    sol   insol  sol   p. sol                                                                              sol   p. sol                                                                              p. sol                                                                              sol                         THF    sol   insol  sol   p. sol                                                                              sol   insol p. sol                                                                              sol                         acetone                                                                              sol   insol  p. sol                                                                              p. sol                                                                              sol   insol p. sol                                                                              p. sol                      MEK    sol   insol  p. sol                                                                              insol sol   sol   insol p. sol                      MIBK   sol   insol  insol insol insol insol insol insol                       EtOAc  sol   insol  insol insol insol insol insol insol                       xylenes                                                                              sol   insol  insol insol insol insol insol insol                       water  p. sol                                                                              p. sol p. sol                                                                              p. sol                                                                              sol   p. sol                                                                              p. sol                                                                              p. sol                      __________________________________________________________________________     MeOH = methanol, EtOH = ethanol, IPA = isopropyl alcohol; PG = propylene      glycol; EB = ethylene glycol nbutyl ether; PTB = propylene glycol             tertbutyl ether; THF =  tetrahydrofuran; MEK = methyl ethyl ketone; MIBK      methyl isobutyl ketone, EtOAc = ethyl acetate.                                Solubility is tested by mixing 10 wt. % polymer in the solvent to give a      clear solution (soluble = sol), a cloudy solution (partly soluble = p.        sol), or two distinct layers (insoluble = insol).                             *Comparative example: poly(allyl alcohol)                                

Example 12. Preparation of a Polyamine Composition

In this example, an allyl alcohol/propoxylated allyl alcohol copolymeris reacted with ammonia to produce a polyamine. Copolymer C (60 g,prepared as in Example 3), ammonia (45 g), and Raney nickel (10 g) arecharged into an one-liter stainless steel reactor. The reactor ispressured with 100 psig of hydrogen, and the contents are heated to 250°C. for 6.5 hours with agitation. During this time, the pressureincreases to about 2500 psig. After cooling, the reactor is vented, andthe product is filtered to remove the nickel catalyst. The expectedproduct is a copolymer of allyl alcohol and propoxylated allyl alcoholin which most of the hydroxyl groups from the copolymer are converted toprimary amino groups.

Example 13. Preparation of an Acrylate Composition

In this example, an allyl alcohol/propoxylated allyl alcohol copolymeris reacted with acrylic acid to make an acrylate composition. CopolymerC (100 g, prepared as in Example 3), acrylic acid (86.5 g), toluene (20g), hydroquinone (0.15 g), and sulfuric acid (0.15 g), are charged intoa reactor equipped with an agitator, thermometer, reflux condenser withDean-Stark trap, and nitrogen inlet. The mixture is heated to reflux(about 100° C. to 115° C.), and water (21.6 g) is removed using thetrap. After no additional water is being produced, the toluene isremoved by vaccum distillation. The expected product is a copolymer ofallyl alcohol and propoxylated allyl alcohol in which most of thehydroxyl groups from the copolymer are converted to acrylate estergroups.

Example 14. Preparation of a Thermoset Polyester Composition

In this example, an allyl alcohol/propoxylated allyl alcohol copolymeris formulated into a thermosetting polyester coating composition.Copolymer C (500 g, as prepared in Example 3) and isophthalic acid (94g) are charged into a reactor and heated to 220° C. while spargingnitrogen through the mixture. After the acid number reaches 60-70 mgKOH/g, adipic acid (73 g), isophthalic acid (60 g), and maleic anhydride(6 g) are added, and the mixture is reheated to 220° C. Heatingcontinues at 220° C. until the acid number drops to 10-12 mg KOH/g.2-Ethoxyethanol acetate (270 g) is then added.

Six hundred grams of the resulting polyester solution is charged into areactor equipped with an agitator, thermometer, reflux condenser,addition funnel, and nitrogen inlet, and the mixture is heated to 120°C. A mixture of 2-hydroxyethyl acrylate (10 g), ethyl acrylate (54 g),styrene (5 g), methyl methacrylate (20 g), methacrylic acid (2 g), anddi-t-butyl peroxide (1.0 g) is charged to the addition funnel. Theacrylate monomer mixture is added to the polyester mixture over 2 h, andis then kept at 120° C. for another hour. t-Butyl perbenzoate (0.2 g) isadded, and the mixture is kept at 120° C. for another 2 h. A second 0.2g portion of t-butyl perbenzoate is added, and heating continues foranother 2 h. The product solution is finally diluted with 1-butanol (30g) and xylene (20 g). This solution is expected to be useful as athermosettable coating composition. The solution can be applied as afilm, and allowed to cure at room temperature or elevated temperature.

Example 15. Preparation of an Alkyd Composition

An alkyd coating composition prepared from an allyl alcohol/propoxylatedallyl alcohol copolymer is described below. Copolymer C (87 g, preparedas described in Example 3), safflower oil (64 g), lithium hydroxide(0.03 g), phthalic anhydride (25.5 g), maleic anhydride (0.22 g),triphenyl phosphite (0.07 g), and xylene (18 g) are charged into areactor equipped with an agitator, thermometer, reflux condenser with aDean-Stark trap, and nitrogen inlet. The mixture is heated to 240° C.,and kept at that temperature until the acid number drops to 10-20 mgKOH/gl. After reaction, xylene is added to dilute the mixture to 50 wt.% solids. This solution is expected to be useful as an alkyd coating.The solution can be applied as a film, and allowed to cure at roomtemperature or at elevated temperature.

The preceding examples are meant as illustrations; the following claimsdefine the scope of the invention.

We claim:
 1. A copolymer which comprises recurring units of:(a) allyl alcohol; and (b) a propoxylated allyl alcohol of the formula:

    CH.sub.2 ═CH--CH.sub.2 --(A).sub.n --OH

in which A is an oxypropylene group, and n, which is the average number of oxypropylene groups in the propoxylated allyl alcohol, has a value within the range of about 1 to about 5; wherein the copolymer has an average hydroxyl functionality within the range of about 2 to about 10, and a number average molecular weight within the range of about 300 to about
 5000. 2. The copolymer of claim 1 wherein n has a value within the range of about 1 to about
 2. 3. The copolymer of claim 1 having from about 1 to about 99 wt. % of allyl alcohol recurring units, and from about 99 to about 1 wt. % of propoxylated allyl alcohol recurring units.
 4. The copolymer of claim 1 having from about 10 to about 85 wt. % of allyl alcohol recurring units, and from about 90 to about 15 wt. % of propoxylated allyl alcohol recurring units.
 5. A copolymer which comprises recurring units of:(a) from about 10 to about 85 wt. % of allyl alcohol; and (b) from about 15 to about 90 wt. % of a propoxylated allyl alcohol of the formula:

    CH.sub.2 ═CH--CH.sub.2 --(A).sub.n --OH

in which A is an oxypropylene group, and n, which is the average number of oxypropylene groups in the propoxylated allyl alcohol, has a value within the range of about 1 to about 2; wherein the copolymer has an average hydroxyl functionality within the range of about 3 to about 6, and a number average molecular weight within the range of about 500 to about 5,000. 